CN1314772C - Polyamide hot melt sol preparation method - Google Patents
Polyamide hot melt sol preparation method Download PDFInfo
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- CN1314772C CN1314772C CNB2005100451011A CN200510045101A CN1314772C CN 1314772 C CN1314772 C CN 1314772C CN B2005100451011 A CNB2005100451011 A CN B2005100451011A CN 200510045101 A CN200510045101 A CN 200510045101A CN 1314772 C CN1314772 C CN 1314772C
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- polyamide hot
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- oxidation inhibitor
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Abstract
The present invention relates to a preparation method for polyamide hot melt adhesive. Dibasic acid and diamine are directly copolymerized and polymerized, and are modified and pulverized to be prepared into polyamide hot melt adhesive. The working procedures of nitrilization, hydrogenation, neutralization, etc. are not needed, and the production technology of the polyamide hot melt adhesive is simplified. The preparation method has the advantages of low equipment requirement, easy raw material obtainment, low cost, and convenient and accurate operation and control. The stable quality of a product is ensured, and the bonding performance of the product is excellent. The polyamide hot melt adhesive not only can be produced in a large scale, but also can be produced in a small scale. The present invention is flexible and convenient, and is easy to popularize and apply.
Description
Technical field
The present invention relates to a kind of preparation method of improved polyamide hot, belong to chemical technology field.
Background technology
Polyamide hot (PA) is a kind of hot melt adhesive that copolymerization such as multiple aliphaticdicarboxylic acid and aliphatic diamine obtain, and is that a kind of high-grade clothing is produced requisite auxiliary material.Polyamide hot has that melt temperature is low is convenient to that processing, bonding strength height, snappiness wear resistance are good, water-fast washes and advantage such as anti-dry-cleaning.Be the best materials of present high-grade clothing fusible interlining and no line sewing clothes.
Utilizing biofermentation technique to produce long-chain biatomic acid is that biofermentation technique is applied to the industrial model of petrochemical complex.Exploitation is the serial polyamide hot of raw material with long-chain diprotic acid such as dodecanedioic acid, undecane dicarboxylic acids, and the needs that domestic high-grade adhesive lining is produced are satisfied in the not only alternative import of product, can also satisfy the requirement of outlet clothes.
At present long carbochain polyamide hot generally adopts long carbochain biatomic acid to obtain long carbon chain nylon salt by nitrilation, hydrogenation, neutralization, obtains polyamide hot in the method with copolymerizations such as hexanolactam, nylon salt and nylon 1010 salt then.Because the performance of long carbochain biatomic acid self, relatively stricter to the requirement of operations such as nitrilation, hydrogenation, neutralization, each operation yield is lower, adds costs such as various starting material, equipment loss, artificial, water power, has increased the cost of polyamide hot virtually; Particularly the determination of acid value of long carbon chain nylon salt does not still effectively solve at present, is difficult for measuring, and has had a strong impact on the control of melt index of polyamide hot-melt adhesive, thereby has affected long carbochain polyamide hot quality of stability.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of improved polyamide hot, technology is simple, and equipment requirements is low, and raw material is easy to get, and cost is low, convenient operation and control, and steady quality, easy to implement.
The preparation method of polyamide hot of the present invention directly carries out the copolymerization polymerization with diamine by diprotic acid, makes through modification, pulverizing again.Not by operations such as nitrilation, hydrogenation, neutralizations, simplified the production technique of polyamide hot, shortened the production cycle, equipment requirements is low, and raw material is easy to get, and cost is low, and convenient operation and control, accurate has guaranteed quality product, steady quality.
Among the present invention:
The ingredients by weight percentage composition is:
Diamine 10～60%
Hexanolactam 0～50%
Nylon salt 0～30%
Nylon 1010 salt 0～30%
Long carbochain biatomic acid 15～60%
Outer adding assistant 0.6～10%.
Wherein:
Long carbochain biatomic acid is C
10～C
16Long carbochain biatomic acid.
Diamine is that one or both or the three kinds of arbitrary proportions in m-xylene diamine, 2 methyl pentamethylenediamine and the hexanediamine mix, and the weight of diamine is formed and is preferably:
M-xylene diamine 0～20%
2 methyl pentamethylenediamine 0～20%
Hexanediamine 0～20%.
Auxiliary agent is made up of molecular weight regulator, oxidation inhibitor, lubricant, anti-hard caking agent, anti, and weight consists of:
Molecular weight regulator 0.1～2%
Oxidation inhibitor 0.1～2%
Lubricant 0.1～0.5%
Anti-hard caking agent 0.1～0.5%
Anti 0.1～3%.
Molecular weight regulator is a kind of in hexanodioic acid, lauric acid, SL-AH or the Glacial acetic acid; Oxidation inhibitor is a kind of in phosphorous acid, antioxidant 1010 or the oxidation inhibitor 1098; Lubricant is a kind of among calcium stearate, Zinic stearas or the EBS; Anti-hard caking agent is an aerosil; The anti auxiliary agent is a low molecular weight polyethylene wax.
Wherein: antioxidant 1010, oxidation inhibitor 1098 are the general commodity of oxidation inhibitor, and the chemical name of antioxidant 1010 is: four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester; The chemical name of oxidation inhibitor 1098 is: N, and N '-two-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) be diamines; EBS has another name called the vinyl bis-stearamides, and chemical name is: N, N '-ethylene bis stearamide.
Lubricant, anti-hard caking agent add when drying or sieving.
The control of polymerization of the present invention and pulverizing requires to require basic identical with the preparation of common polyamide hot, the polymeric temperature is 180～250 ℃, rise to 180 ℃, begin pressurize when pressure reaches 1.2MPa, time is 1～2 hour, in 2 hours, pressure is evenly let out to normal pressure then, directly vacuumized behind normal pressure emptying 1～2 hour or the normal pressure then and got final product discharging in 0.5～1 hour.
Polyamide hot is dropped into autoclave, add the alcoholic solvent dissolving, precipitating obtains the polyamide hot powder then, through washing, oven dry, or with after the oven dry of polyamide hot particle, drop into the deep cooling pulverizer, use cooled with liquid nitrogen, carry out deep cooling and pulverize, under air-tight state, polyamide hot powder after pulverizing is risen to room temperature, sieve then polyamide hot.
The preparation method of polyamide hot of the present invention, production technique is simple, and equipment requirements is low, and raw material is easy to get, cost is low, and convenient operation and control, accurate has guaranteed the stable product quality, and the product adhesiveproperties is good, both can be mass-produced, but also small serial production is flexible, is easy to apply.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Polymerization: SL-AH 20kg, 2 methyl pentamethylenediamine 10kg, hexanolactam 40kg, nylon 1010 salt 30kg and hexanodioic acid 1kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, and behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 180 ℃, when pressure reaches 1.2MPa, the beginning pressurize, after 2 hours the beginning even pressure release, the time is 2 hours, normal pressure after 1 hour discharging get polyamide hot.
Pulverize: polyamide hot is dropped into autoclave, add ethanol (according to different granularity demands, need different consumptions, consumption is big, the fine powder content height, otherwise, meal content height, generally be controlled at polyamide hot and alcoholic acid mass ratio and be and got final product in 1: 3～1: 5) dissolving, 150 ℃ of temperature, under the pressure 1.0MPa, polyamide hot is dissolved in the ethanol, then through cooling, precipitating obtains the polyamide hot powder, after distilled water, the conventional washing of softening water or deionized water, oven dry, add 0.1% calcium stearate and 0.3% aerosil sieves, the polyamide hot finished product.
Embodiment 2
Polymerization: SL-AH 30kg, m-xylene diamine 18kg, hexanolactam 30kg, nylon salt 22kg and hexanodioic acid 1kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, and behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 190 ℃, when pressure reaches 1.2MPa, the beginning pressurize, after 2 hours the beginning even pressure release, the time is 2 hours, normal pressure after 1 hour discharging get polyamide hot.
Pulverize: after 70 ℃ oven dry of polyamide hot, drop into the deep cooling pulverizer, arrive-130 ℃ with cooled with liquid nitrogen, carrying out deep cooling pulverizes, under air-tight state, polyamide hot powder after pulverizing is risen to room temperature, adds 0.1% calcium stearate then and 0.3% aerosil sieves, the polyamide hot finished product.
Embodiment 3
Polymerization: SL-AH 60kg, 2 methyl pentamethylenediamine 20kg, hexanolactam 10kg, hexanediamine 10kg and lauric acid 1.5kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, and behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 190 ℃, when pressure reaches 1.3MPa, the beginning pressurize, after 2 hours the beginning even pressure release, the time is 2 hours, normal pressure after 1 hour discharging get polyamide hot.
Pulverize: after 70 ℃ oven dry of polyamide hot, drop into the deep cooling pulverizer, arrive-120 ℃ with cooled with liquid nitrogen, carrying out deep cooling pulverizes, under air-tight state, the polyamide hot powder rises to room temperature before will pulverizing the back, adds 0.1% Zinic stearas then and 0.3% aerosil sieves, the polyamide hot finished product.
Embodiment 4
Polymerization: 11 carbon dicarboxylic acid 28kg, 2 methyl pentamethylenediamine 15kg, hexanolactam 25kg, nylon 1010 salt 32kg and Glacial acetic acid 0.6kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 200 ℃, when pressure reaches 1.2MPa, the beginning pressurize, after 1.5 hours the beginning even pressure release, the time is 2 hours, normal pressure after 1 hour discharging get polyamide hot.
Pulverize: after 70 ℃ oven dry of polyamide hot, drop into the deep cooling pulverizer, arrive-150 ℃ with cooled with liquid nitrogen, carrying out deep cooling pulverizes, under air-tight state, polyamide hot powder after pulverizing is risen to room temperature, adds 0.1%EBS then and 0.3% aerosil sieves, the polyamide hot finished product.
Embodiment 5
Polymerization: tridecanyldicarboxylic acid 31kg, 2 methyl pentamethylenediamine 16kg, hexanolactam 30kg, nylon 1010 salt 23kg and SL-AH 1.6kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 180 ℃, when pressure reaches 1.2MPa, the beginning pressurize, after 2 hours the beginning even pressure release, the time is 2 hours, normal pressure after 2 hours discharging get polyamide hot.
Pulverize: polyamide hot is dropped into autoclave, add propyl carbinol, polyamide hot is dissolved in the propyl carbinol, obtain the polyamide hot powder through cooling, precipitating then, after washing, add 0.2% calcium stearate and the oven dry of 0.3% aerosil, sieve, the polyamide hot finished product.
Embodiment 6
Polymerization: SL-AH 50kg, 2 methyl pentamethylenediamine 25kg, hexanolactam 15kg, nylon salt 10kg and SL-AH 1.2kg, phosphorous acid 100g, polyethylene wax 200g are dropped into polymermaking autoclave, behind the carbon dioxide replacement, the energising heating is opened and is stirred.When temperature reach 185 ℃, when pressure reaches 1.2MPa, the beginning pressurize, after 1.5 hours the beginning even pressure release, the time is 2 hours, normal pressure after 1.5 hours discharging get polyamide hot.
Pulverize: polyamide hot is dropped into autoclave, add ethylene glycol, under High Temperature High Pressure, polyamide hot is dissolved in the ethylene glycol, obtain the polyamide hot powder through cooling, precipitating then, after washing, add 0.1% calcium stearate and the oven dry of 0.3% aerosil, sieve, the polyamide hot finished product.
The fusing point of polyamide hot and performance see Table 1 among each embodiment.
The fusing point of table 1, polyamide hot and performance table
| Embodiment | Fusing point (℃) | Initial stage stripping strength (kgf/2.5cm) | Wash 1 stripping strength (kgf/2.5cm) | Wash 5 stripping strengths (kgf/2.5cm) | Dry-clean 1 stripping strength (kgf/2.5cm) | Dry-clean 5 stripping strengths (kgf/2.5cm) |
| 1 | 120 | 4.2 | 4.0 | 3.8 | 4.2 | 4.1 |
| 2 | 125 | 4.5 | 4.4 | 4.2 | 4.5 | 4.5 |
| 3 | 106 | 5.0 | 4.7 | 4.6 | 5.0 | 4.8 |
| 4 | 114 | 4.6 | 4.4 | 4.3 | 4.6 | 4.6 |
| 5 | 118 | 4.9 | 4.6 | 4.2 | 4.9 | 4.9 |
| 6 | 130 | 5.3 | 5.1 | 4.5 | 5.3 | 5.3 |
Claims (1)
1, a kind of preparation method of polyamide hot is characterized in that directly carrying out the copolymerization polymerization with diamine by diprotic acid, makes through modification, pulverizing again, and its ingredients by weight percentage composition is:
Diamine 10～60%
Hexanolactam 0～50%
Nylon salt 0～30%
Nylon 1010 salt 0～30%
Long carbochain biatomic acid 15～60%
Outer adding assistant 0.6～10%;
Wherein:
Long carbochain biatomic acid is C
10～C
16Long carbochain biatomic acid;
Diamine is a kind of in m-xylene diamine or the 2 methyl pentamethylenediamine;
Auxiliary agent is made up of molecular weight regulator, oxidation inhibitor, lubricant, anti-hard caking agent, anti, and the weight of auxiliary agent consists of:
Molecular weight regulator 0.1～2%
Oxidation inhibitor 0.1～2%
Lubricant 0.1～0.5%
Anti-hard caking agent 0.1～0.5%
Anti 0.1～3%;
Molecular weight regulator is a kind of in hexanodioic acid, lauric acid, SL-AH or the Glacial acetic acid; Oxidation inhibitor is a kind of in phosphorous acid, antioxidant 1010 or the oxidation inhibitor 1098; Lubricant is calcium stearate, Zinic stearas or N, a kind of in N '-ethylene bis stearamide; Anti-hard caking agent is an aerosil; The anti auxiliary agent is a low molecular weight polyethylene wax.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100451011A CN1314772C (en) | 2005-11-11 | 2005-11-11 | Polyamide hot melt sol preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100451011A CN1314772C (en) | 2005-11-11 | 2005-11-11 | Polyamide hot melt sol preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1763146A CN1763146A (en) | 2006-04-26 |
| CN1314772C true CN1314772C (en) | 2007-05-09 |
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| CNB2005100451011A Expired - Fee Related CN1314772C (en) | 2005-11-11 | 2005-11-11 | Polyamide hot melt sol preparation method |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102744802A (en) * | 2012-07-09 | 2012-10-24 | 东莞芳言塑胶科技有限公司 | Method for processing hot melt adhesive waste products into raw material |
| CN103254868B (en) * | 2013-05-17 | 2014-12-10 | 上海凯赛生物技术研发中心有限公司 | Hot melt adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357589A (en) * | 2000-12-12 | 2002-07-10 | 梁子材 | Multi-purpose polyamide hot melt adhesive and its prepn |
| CN1415686A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for preparing polyamide hot-melt adhesive |
| US6590063B2 (en) * | 2000-05-10 | 2003-07-08 | Ems-Chemie Ag | Low-melting copolyamide and their use as hot-melt adhesives |
| CN1597826A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590063B2 (en) * | 2000-05-10 | 2003-07-08 | Ems-Chemie Ag | Low-melting copolyamide and their use as hot-melt adhesives |
| CN1357589A (en) * | 2000-12-12 | 2002-07-10 | 梁子材 | Multi-purpose polyamide hot melt adhesive and its prepn |
| CN1415686A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for preparing polyamide hot-melt adhesive |
| CN1597826A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Thermosol of polyamide and preparation process thereof |
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Owner name: GUANGTONG CHEMICAL CO. LTD., ZIBO Effective date: 20121015 Owner name: SHANDONG GUANGYIN NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: GUANGTONG CHEMICAL CO. LTD., ZIBO Effective date: 20121015 |
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Effective date of registration: 20121015 Address after: 255086 Shandong city of Zibo province high tech Zone Min Xiang Road and 500 meters north of the intersection of East Industrial Road Patentee after: Shandong Guangyin New Materials Co., Ltd. Patentee after: Guangtong Chemical Co., Ltd., Zibo Address before: 255144 Longquan Town, Zichuan District, Shandong, Zibo Patentee before: Guangtong Chemical Co., Ltd., Zibo |
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